Synthetic resin and method of producing



' Patented May 18, 1937 UNITED STATES PATENT orrlce snr'rnn'no nas m AND rm'rnon or rnonncmo Ema 6. Peterson, Wilmington, Dcl., assignor to Hercules Powder Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application January 12 1935. Serial No. 1.50:

as claims. (or. zoo-s) J This invention relates to a new composition within about the range 182 C.-190 C. is used, of matter and method for its production. however, the product will largely involve the re- In accordance' with this invention a novel action product 01' maleic anhydride and terpinosynthetic resin having characteristics renderlane, with possible admixture of other reaction 5 ing it valuable for use variously in the comproducts in relatively small amount. 5 mercial arts is prepared by reacting together In preparing the synthetic resin in accordance maleic anhydride, rosin or abietic acid, and a with this invention the reagents may be reacted terpene-hydrocarbon possessing no conjugated in widely varying proportions depending. upon system of double bonds or equivalently a terthe physical characteristics desired for the resin none cut comprising largely one or a mixture of product with consideration tov the useto which 10 p e ydr a s p ssessing no conjugated it is to be put. Generally speaking, it is desystem of double bonds. sirable to employ maleic anhydride' approxi- Generally speaking, the terpene hydrocarbons mately in theproportion necessary to completenot having any conjugated system of double ly satisfy the reactivity a: the terpene hydrobonds comprise alpha-pinene (B, P. about 153 carbon or hydrocarbons and the abietic acid. 1 C.--157 C.), beta-pinene (B. P. about 160 Thus, for example, with use of relatively large C.-168 C.), dipentene (B. P. about 170 C.-178 amounts of the terpene hydrocarbon the prod- C.)'and its 1somers,asdand l-limonene, and teruct is soft and tough, with more abietic acid pinolene (B. P. about 183 C.-185 C.) in proportion to the terpene hydrocarbon, the

The term terpene hydrocarbon as used product is hard and brittle and so on, it being 20 throughout this specification refers solely to clear that by varying the proportions and those terpene hydrocarbons having the formula amounts. of the reagents, products having vary CmHu, often known as true terpenes or terpenes ing characteristics may be produced.

pr pe I In preparing the improved synthetic resin the g As equivalent for the several hydrocarbons in reagents will be reacted in the presence of heat.

relatively pure state, terpene cuts relatively However, it will be expressly understood that richin the hydrocarbons, respectively, may be any means for eflecting the reaction is contemutilized. Thus, a terpene cut boiling within plated as within the scope of this invention.

about the range 150 C. 165 C. will be relatively Any suitable temperature may be used, though a rich in alpha-pinene. A terpene cut boiling temperature within the range say about-125 C. 30 within about the range 160' C.-170 C. will be rel- 250 C. is desirable. The reaction will usually atively rich in beta-pinne, while also containbe carried out under atmospheric pressure, but ing some alpha-pinene. A terpene cut boiling with variations of temperature, procedure under within about the range 150 C.-170.C. will be reduced or super-pressure will obviously be 5 relatively rich in both alpha-. and beta-piene. within the scope of my invention. The produc- A terpene cut boiling within about the range tion of the resin in accordance with this inven- 170" C.-178 C. will be relatively rich in dipention may be carried'out in any suitable appatene, while a terpene cut. boiling within about ratus, as am; suitable container in which the the range 182 C.-190 C. will be relatively rich reagents may be heated. On completion of the 40 in terpinolene. Terpene cuts relatively rich reaction any volatile unreacted matter may be 40 in the several hydrocarbons not having any removed or separated from the product by the conjugated system of double bonds or cuts relaapplication of a vacuum to the reaction mass tively rich in mixtures thereof will variously con- .betore cooling. V tain other terpenes or impurities, which, how- As a specific illustration oi the practical adapever, will not efl'ect the carrying out of the tation of my invention embodying the use of 45 process in accordance with this invention for 'terpinolene, or equivalently a terpene cut boiling the production of the various products contem at 182 C.-190 C., parts by weight of tere plated and which may readily be separated pinolene, 165 parts of abietic acid and 98 parts fromthe ilnal product. Thus, for example, a, of maleic anhydride-are heated together .ata 50 terpene cut boiling within the range 182 C.-190 temperature of approximately 200 C. for about 50 mass C. consisting largely of terpinolene (B. P. 183 3 hours... The pressure on the reaction C.-185 C.), will contain certain amounts 01 is then reduced to" about 15 mm. of mercury terpene alcohols, such as fenchyl alcohol and and any unreacted maleic anhydride'and the borneol, and also will contain some plnen'e and inert ingredients associated with the terpino- 55. some dipentene. Where a terpene cut boiling lene distilled ofl. i 55 The reaction product obtained by the above procedure will be found to have a direct acid number of about 250, saponification value of about 400, melting point (drop method) of about 100 C. and a rhodanometric iodine value of 10.

As a specific illustration of procedure involving the use of dipentene, or equivalently a terpene cut boiling at 170 C.178 C., 100 parts by weight of dipentene, 165 parts of abietic acid and 98 parts of maleic anhydride are heated together at a temperature of approximately 200 C. for about 3 hours. The pressure on the reaction mass is then reduced to about 15 mm. of mercury and any unreacted maleic anhydride and the inert ingredients associated with the dipentene are distilled off.

The reaction product obtained by the above procedure will be found to have a direct acid number of about 260, saponification value of about 415, melting point (drop method) of about 95 C. and a rhodanometric iodine value of 23.

As illustrative of procedure in accordance with this invention using alpha-pinene, or equivalently a terpene cut boiling at C.- C., 100 parts by weight of alpha-pinene, 165 parts of abietic acid and 98 parts of maleic anhydride are heated together at a temperature of approximately 200 C., for about 3 hours. The pressure on the reaction mass is then reduced to about 15 mm. of mercury and any unreacted maleic anhydride and the inert ingredients associated with the pinene are distilled off.

The reaction product obtained by the above procedure will be found to have a direct acid number of about 240, saponification value of about 385, melting point (drop method) of about 85 C. and a rhodanometric iodine value of 25.

In place of alpha-pinene, beta-pinene, or equivalently aterpene cut boiling at 160 C.- C. may be used.

As illustrative of various amounts of the several reagents which may be reacted to produce resins in accordance with this invention, for example, the reagents may be reacted in the various proportions given in the following tables:

Terplnolene Rosin Pam by weight i! weiahi Paris by weight 160 20 98 42 93 130 3 98 43 250 98 Dipentene, p -p e. or Rosin Malm betalu anhydride Part! 0!! Weight Parts by weight Parts by wpi ht The several reagents in, for example, the proportion given in the above table may be reacted in any suitable container, at a temperature say within the range 150 C.-250 C. for say one to five hours. Volatile unreacted matter may, as has been indicated, be removed on completion of the reaction by reducing the pressure in the reaction mass before cooling.

The product in accordance with this invention will be found to be a highly acidic resin, capable. for example, of reacting with alcohols, as for methyl, ethyl, butyl be used equivalently.

example, polyhydric alcohols as glycerol, aliphatic glycols, etc., to yield synthetic gums or resins which have characteristics making them highly desirable for use, for example, in varnishes, lacquers, etc.

No claim is made in this application to those synthetic resins described herein formed from dipentene or its isomers, since such resins are the invention of and are claimed by Hayward H. Coburn in an application, Serial No. 694,063, filed October 18, 1933 now Patent 2,047,004.

No claim is made in this application to those synthetic resins described herein formed from alphaor beta-pinene, since such resins are the invention of and are claimed by Irvin W. Humphrey in an application, Serial No. 688,988, filed September 11, 1933 now Patent 1,993,036.

As an example of the esterification of the product obtained in one of the specific illustrations above with a polyhydric alcohol the following is 100 parts by weight of the reaction product from terpinolene described above and 58 parts of glycerol may be heated at a temperature of 230 C.-240 C. for 6 hours. The resulting resin has an acid value of 40 and a melting point (drop method) of approximately 100 C. It is highly desirable for use in lacquers and varnishes. Various modifying agents such as, for example, drying or semi-drying oils or their acids may be added.

Esteriflcation with monohydric alcohols as alcohols, etc., may likewise be carried out, in the case of low-boiling alcohols preferably under pressure.

It will be understood that in producing the compositions comprising this invention vabietic acid as such may be used or rosin, either wood or gum, preferably high in abietic acid content may It is also contemplated to use in place of abietic acid other compounds containing the abietyl radical such as, for example, esters of abietic' acid with a monohydric alcohol as methyl, ethyl, propyl alcohols, glycol, glycerol, etc. When an ester .of abietic acid is employed the acidity of the reaction product is lower due to the fact that one carboxyl group is esterified.

As a specific illustration, for example, of the use of an ester of abietic acid, 85 parts by weight of terpinolene, or equivalently a terpene cut boiling at 182 C.- C.-, 158 parts of methyl abietate and 98 parts of maleic anhydride are heated together at a temperature of about 200 C. forthree hours. The pressure is then reduced to 15 mm. of mercury and the excess of maleic anhydride and the inert ingredients associated with the terpinolene are removed.

The acidic resin produced in accordance with i this invention may not be completely saturated product 01' an alcohol not of an alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene hydrocarbon of the formula CmHw and possessing no conjugated system of double bonds. maleic anhydride'and a compound containing the abietyl radical.

2. A synthetic resin comprising a reaction and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene hydrocarbon oi the formula CmHis and possessing no conjugatedsystem of double bonds. maleic anhydride and abietic acid.

3. A synthetic resin comprising a reaction product of an alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene hydrocarbon of the formula CmHis and possessing no conjugated system of double bonds, maleic anhydride and an abietic acid ester.

4. A synthetic resin comprising a reaction product of an alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene hydrocarbon of the formula conjugated system CioI-Im'and possessing no conjugated system of double bonds, maleic anhydride and rosin.

5. A synthetic resin comprising a reaction product of a polyhydric alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene hydrocarbon of the formula (2101-116 and possessing no of double bonds, maleic anhydride and a compound containing the abietyl radical.

system of double bonds, maleic anhydride and a compound containing the abietyl radical.

7. A synthetic resin comprising a reaction product of glycerol and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene hydrocarbon of the formula CwHis and double bonds, maleic anhydride and a compound containing the abietyl radical.

3. A synthetic resin comprising a reaction duct double bonds, maleic anhydride and a compound containing the abietyl radical.

10. A synthetic resin produced by combining a polyhydric alcohol, a drying oil fatty acid, and a reaction product formed by simultaneously combining a terpene hydrocarbon of the formula ClOHlB and containing the abietyl radical.

11. The method for producing a synthetic resin which includes simultaneously reacting a terpene hydrocarbon of the formula CmHw and possessing no conjugated system of double bonds, maleic anhydride and a compound containing product-of an alcohol and an the abietyl radical and of a character such that the abietyl radical is available for reaction, and then reacting the product of said reaction with an alcohol. v

12. A synthetic resin comprising a reaction product of an alcohol and an acidic composition comprising areaction product of the simultaneous reaction of terpinolene, maleic anhydride and a compound containing the abietyl radical.

13. A synthetic resin comprising a reaction product of an alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of terpinolene, maleic anhydride and abietic acid. a

14. A synthetic resin comprising a reaction acidic composition comprising a reactionv product of the simultaneous reaction of terpinolene, maleic anhydride and an abietic acid ester.

15. A synthetic resin comprising a reaction product of an alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of terpinolene, maleic anhydride and rosin. a

'16. A synthetic resin comprising a reaction product of a polyhydri'c alcohol and an acidic composition comprising a reaction product of the simultaneous reaction 01 terpinolene, maleic anhydride and a compound containing the abietyl radical.

17. A synthetic resin comprising a reaction product of a monohydric alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of terpinolene, maleic anhydride and a compound containing the abietyl radical.

18. A synthetic resin comprising a reaction product of glycerol and an acidic composition comprisinga reaction product of the simultaneous reaction of terpinolene, maleic anhydride and a compound containing the abietyl radical.

19. A synthetic resin comprising a reaction product of an aliphatic glycol and an acidic composition comprising-a reaction product of the simultaneous reaction of terpinolene, maleic anhydride and a compound containing the abietyl radical.

20. A synthetic product of .the simuland then reacting the product of said reaction with an alcohol.

23. A coating composition comprising a reacthe 'abietyl radical; and a solvent.

24. A coating composition comprising a reaction product of an alcohol and an acidic comthe simultaneous reaction of a terpene hydrocarbon of the formula C10H1s resin comprising a reactionproduct of ethyl alcohol and an acidic composiand possessing no conjugated system 0! double bonds, maleic anhydride and a compound containing the abietyl radical; a non-volatile lacquer ingredient and a solvent.

25. A coating composition comprising a reaction product of an alcohol and an acidic composition formed by the simultaneous reaction of a terpene hydrocarbon of the formula CioHis and possessing no coniugated system of double 1() bonds, maleic anhydride and a compound containing the abietyl radical; a. non-volatile varnish ingredient and a solvent.

26. A synthetic resin comprising a reaction product of an alcohol and an acidic composition comprising a reaction product of the simultaneous reaction of a terpene cut boiling within the range 182-190 C., maleic anhydride and a. compound containing the abietyl radical.

ERNEST G. PETERSON. 

